Dyestuffs of the dibenzanthrone series



Patented June 18, 1935 UNITED STATE rAsNr cries DYE STUFFS 0F THE DIBENZANTHRONE SERIE S Delaware No Drawing. Original application May 2, 1930,

Serial No. 449,355. Divided and this application August 3, 1934, Elerial No. 738,372

9 Claims.

This invention relates to novel vat dyes of the dibenzanthrone series. More particularly, this invention deals with novel dyestuffs of the dioem zanthrone series obtainable by alkali-fusion of the novel phenyl-benzanthrones described and claimed in the copending application, Serial No. 449,355, of which'the instant application is a division.

It is an object of this invention to produce new vat dyestuffs of the dibenzanthrone series. Other and further important objects of this invention will appear as the description proceeds.

These objects are accomplished by the present invention whereby beta-phenyl-anthraquinone is first condensed with sulfuric acid, glycerine, and a metailic reducing agent, according to the process of said copending application, to produce betaphenyl-benzanthrone. The latter is then condensed by the aid of alcoholic alkali melts to produce the new dyestuffs.

The initial beta-phenyl-anthraquinone may contain substituents in the phenyl nucleus, such as halogen or hydroxy. In. these cases the intermediate phenyl-benzanthrone and the final cliphenyl-dibenzanthrone also contain the same substituents.

The condensation of phenyl-anthraquinone with glycerine, as above mentioned, may lead to a mixture of isomeric phenyl-benzanthrones instead of to a single compound. These may or may not be separated before alkali-fusion, as desired.

Without limiting this invention to any particular procedure, the following examples are given to illustrate the preferred mode of operation. Parts are by weight.

Example I 100 parts of para-chloro-beta-phenyl-anthraquinone are dissolved in 1500 parts of -100% sulfuric acid. To this solution is added a sufiicient quantity of water to reduce the acidity approximately to 80-83 The temperature is then raised to 1l2-115 C. and maintained at this level while '75 to parts of glycerine and 25 to 35 parts of copper powder are added simultaneously and at such a rate that both reagents will be incorporated into the charge in a period of two to three hours. When this has been accomplished the temperature is raised to 118-120" C. and maintained at this point until none of the initial material, para-chloro-beta phenyl-anthraquinone,

can be detected. The melt is then diluted by pouring the same into a large volume of water. The precipitate is filtered ofi, washed until acidfree and then subjected toan alkaline extraction to remove alkaline water-soluble impurities.

The product thus obtained consists of a dark greenishyellow powder which consists of at least three isomeric products, which can be separated by fractional crystallization from alcohol and benzene. One isomeric form is soluble in cold alcohol, another in hot alcohol and still another in benzene. The recrystallized products are yellow to greenish-yellow compounds having melting points as follows:

(a) Easily soluble product lvi. P. 131.8-13i.i C. (1)) Less easily soluble prod- 1 uct M.P. 102.4-103.6C. (c) Benzene soluble product M. P. 160-162 C.

100 parts of the above product (either separated or unseparated) are introduced into an alcoholic potash melt (460 part of EOE-{A00 parts of ethanol) at 100 C. under good agitation. The temperature is raised to -460 C. and maintained at this level for approximately four hours. The melt is then poured into a large volume of water. The blue-black dyestufi which separates, is oxidized by aeration, filtered, washed free of alkali and dried. The dried material consists of a dark powder, giving dull greenish-blue sulfuric acid solutions having a brown fluorescence. It dyes from a blue hydrosulfite vat in greenish-blue or steel-blue shades, depending upon which of the several fractional products above areused. These new dyestuffs diifer from the well-known dibenzanthrone products (violanthrone and isoviolanthrone) in that they they tend to give greenish shades rather than dark blue and violet.

Example II The procedure is the same as in Example I, except that ortho-chloro-beta-phenylanthraquinone is used as initial material. The intermediate and final products obtained are in general similar to those obtained in Example I.

Example III The procedure is the same as in Example I, except that meta-chloro-beta-pheny1-anthraquinone is used as initial material. The interwherein J stands for hydrogen or a simple inert substituent, the phenyl nuclei being positioned in the anthrone portions of the molecule.

2. A diphenyl-dibenzanthrone, the phenyl nuclei being positioned in the anthrone portions of the molecule. I

3. Dichloro-diphenyl-dibenzanthrone.

4. The. dyestuil resulting by subjecting to caustic fusion the mixed product resulting from rewherein J stands for hydrogen, or a simple inert substituent, such as halogen or hydroxy.

The condensation of the beta-phenyleanthraquinone is not limited to copper as a reducing agent since other metal substances, for example,

iron and aluminum, may be used. The. various isomers of the beta-phenyl-anthraquinone-glycerine condensation will ordinarily be separated and subsequently converted to the dyestuft but the group mixture of isomers obtained (for instance in Example I) can be treated directly in an alcoholic potash melt to produce a valuable dyestuff material consisting of a mixture of compounds.

The dyestufis of this invention are characterized by better shades than present well-known dibenzanthrone colors. For instance the new dyestufis obtained according' to Example I, when applied to cotton produce much bluer shades than are now known.

The halogen beta-phenyl-benzanthrone and the corresponding dibenzanthrone derivatives are further useful in that they are capable of condensation with primary amino compounds.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended patent claims.

What isclaimed is:

1. A dyestuff of the general formula acting a beta-phenyl-anthraquinone with glycerine, sulfuric acid and a reducing metal.

5. The process of producing a dyestuff, which comprises subjecting to caustic fusion a betaphenyl-benzanthrone.

6. The process of producing a dyestuif, which comprises heating a beta-phenyl-benzanthrone with alcoholic potash to form a diphenyl-dibenzanthrone compound, diluting the reaction mass in water, and recovering the precipitated dyestufi.

7. The process of producing a dyestuff, which comprises subjecting to caustic fusion a chlorophenyl-benzanthrone.

8. The process of producing a dyestuff, which comprises subjecting to caustic fusion the mixed product resulting from reacting a beta-phenylanthraquinone with glycerine, sulfuric acid and a reducing metal.

9. The process which comprises heating substantially parts of a chloro-beta-phenylbenzanthrone with substantially 400 parts of caustic potash and 400 parts of ethanol at a temperature of about to C. for several hours, drowning the reaction mass in water, aerprecipitated dyestufi.

ALEXANDER J. WUER'IZ. EVA P. BISHOP, WILMINGTON TRUST CO., TILGI-IMAN JOHNSTON,

' Vice President, Executors of the Estate of Oakley M. Bishop, De-

ceased.

ating the resulting suspension, and recovering the 6 

